JP5286679B2 - Adhesive composition for electronic parts and adhesive sheet for electronic parts using the same - Google Patents

Description

  The present invention relates to an adhesive composition for electronic parts. More specifically, a tape automated bonding (TAB) pattern processing tape, a substrate for connecting a semiconductor integrated circuit such as an interposer for a ball grid array (BGA) package, and a lead frame fixing tape, which are used when mounting a semiconductor integrated circuit. Adhesives between electronic parts such as LOC fixing tapes and semiconductor elements and supporting members such as lead frames and insulating support substrates, ie die bonding materials, heat spreaders, reinforcing plates, shielding material adhesives, solder resists, optical path bonding adhesives Adhesives for electronic parts suitable for producing adhesives, optical part assembly adhesives, optical adhesives such as LED sealants, anisotropic conductive films, copper-clad laminates, coverlays, and the like Adhesive sheet for electronic parts, tape with adhesive for electronic parts, semiconductor integration Road connection substrate relates to a copper-clad laminate.

  In recent years, downsizing and increasing the density of electronic devices are rapidly progressing. Since the adhesive composition for electronic parts used in electronic devices often remains in the package as an adhesive, it is required to satisfy various properties such as adhesiveness, heat resistance, and insulation durability. Yes.

  Until now, as adhesive sheets for electronic parts, for example, tapes with an adhesive having an adhesive layer containing an epoxy resin and a polyamide resin (for example, see Patent Documents 1 and 2) have been proposed, but insulation durability is poor. It was enough.

As a method for improving the insulation durability under high temperature and high humidity, the crosslink density of the adhesive is increased. However, there is a problem that the shrinkage at the time of curing the adhesive is increased and warping occurs. Therefore, an adhesive using a flexible polyether ester amide resin has been proposed in order to reduce warpage (see, for example, Patent Document 3). Although the warpage is reduced by this method, there is a problem that the insulation durability under high temperature and high humidity conditions is insufficient as the circuit pattern becomes thinner.
JP 9-321094 A (Claim 1) JP 2002-33354 A (Claim 1) JP 2001-354938 A (Claim 2)

  In view of the above problems, an object of the present invention is to provide an adhesive composition for electronic components that forms an adhesive layer that has excellent adhesion durability at high temperatures and insulation durability at high temperatures and high humidity, and has little warpage. To do.

The present invention relates to bis (3-aminopropyl) phosphate, phosphoric acid bisaminobutyl ester, bis (4-aminophenyl) pheosphate, bis (4-aminophenyl) phosphine, bis (3-amino-4) -Hydroxyphenyl) phosphine, bis (3-aminopropyl) sulfide, bis (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfone, bis (3-amino-4-hydroxyphenyl) sulfone, 4,4 ' -Bis (2-amino-6-methoxypyrimidyl) disulfone, 1,2-bis (2-aminoethoxy) ethane, 1,4-bis (4-aminophenoxy) benzene, bis (3-aminopropyl) ether And 4,4′-bis (4-aminophenoxy) biphenyl A structural unit composed of the above amine and dimer acid, one or more diamines selected from ethylenediamine, hexamethylenediamine, piperazine and 1,4-bis (aminomethyl) cyclohexane, and diethylenetriamine, N, N′-bis ( One or more aliphatic amines selected from one or more polyamines selected from 3-aminopropyl) ethylenediamine, N, N′-bis (2-aminoethyl) -1,3-propanediamine and ethylenediaminehexamethylenetetramine and dimer acid It is the adhesive composition for electronic components characterized by containing the polyamide resin which is a block copolymer which has a structural unit comprised from these, and a thermosetting resin.

  ADVANTAGE OF THE INVENTION According to this invention, the adhesive composition for electronic components which is excellent in the adhesive durability in high temperature, and the insulation durability in high temperature, high humidity, and forms an adhesive layer with few curvature, and an adhesive sheet for electronic components using the same Can be obtained. By using the adhesive sheet for electronic parts of the present invention, a tape with an adhesive for electronic parts, a substrate for connecting a semiconductor integrated circuit, a copper-clad laminate, and a semiconductor device that can be processed at high temperatures can be produced industrially advantageously. Thus, the reliability of the obtained semiconductor device can be improved.

  The present invention will be described in detail below.

The adhesive composition for electronic parts of the present invention (hereinafter sometimes referred to as an adhesive composition) includes bis (3-aminopropyl) phosphate, phosphoric acid bisaminobutyl ester, and bis (4-aminophenyl). Feosfate, bis (4-aminophenyl) phosphine, bis (3-amino-4-hydroxyphenyl) phosphine, bis (3-aminopropyl) sulfide, bis (4-aminophenyl) sulfide, bis (4-aminophenyl) ) Sulfone, bis (3-amino-4-hydroxyphenyl) sulfone, 4,4′-bis (2-amino-6-methoxypyrimidyl) disulfone, 1,2-bis (2-aminoethoxy) ethane, 1 , 4-bis (4-aminophenoxy) benzene, bis (3-aminopropyl) ether and And a structural unit composed of one or more amines selected from 4,4′-bis (4-aminophenoxy) biphenyl and dimer acid, ethylenediamine, hexamethylenediamine, piperazine and 1,4-bis (aminomethyl) From one or more diamines selected from cyclohexane and diethylenetriamine, N, N′-bis (3-aminopropyl) ethylenediamine, N, N′-bis (2-aminoethyl) -1,3-propanediamine and ethylenediaminehexamethylenetetramine It contains a polyamide resin that is a block copolymer having a structural unit composed of one or more aliphatic amines selected from one or more selected polyamines and a dimer acid . It is preferable to have such a structural unit in an amount of 3 mol% or more in all structural units of the polyamide resin.

  The polyamide resin is obtained by polycondensation of an acid and an amine. In the present invention, it is necessary to use dimer acid as the acid component. The polyamide resin containing dimer acid is excellent in terms of flexibility, low hygroscopicity, and solubility. For this reason, the adhesiveness of the obtained adhesive composition, the adhesive durability under high temperature, and the insulation durability under high temperature and high humidity are improved. The dimer acid is preferably obtained from an unsaturated fatty acid having 20 to 50 carbon atoms, and examples thereof include dimerized unsaturated fatty acids such as palmitic acid, oleic acid, linoleic acid, and linolenic acid. Two or more of these may be used. Further, dicarboxylic acids other than dimer acid such as adipic acid, azelaic acid, and sebacic acid may be copolymerized. In that case, the content of dimer acid is preferably 60% by weight or more in the total acid component.

  On the other hand, the amine component needs to have at least one atom selected from phosphorus, sulfur, and oxygen. Phosphorus and sulfur are activated by increasing the free volume of the polyamide resin due to the size of the atoms, and as a result, the molecular motion is activated. As a result, the flexibility is improved, and adhesion with excellent adhesion and low warpage is achieved. An agent composition can be obtained. In the case of oxygen atoms, since the rotation of the molecules is promoted by having oxygen atoms in the polyamide main chain, the same effect can be obtained. In the present invention, it is important to have phosphorus, sulfur or oxygen in the amine component. By using such an amine component and dimer acid, it is possible to achieve both high insulation durability under high temperature and high humidity, adhesion durability, and low warpage.

Further, the amine component needs to have two or more amino groups in one molecule, and polyamines such as triamine and tetramine can also be used. The need use in the present invention, phosphorus, sulfur, as the amine component having at least one atom and 2 or more amino groups selected from oxygen, bis (3-aminopropyl) phosphate, phosphoenolpyruvate butyric acid bis-amino-butyl ester Bis (4-aminophenyl) pheosphate, bis (4-aminophenyl) phosphine, bis (3-amino-4-hydroxyphenyl) phosphine, bis (3-aminopropyl) sulfide, bis (4-aminophenyl) Sulfide, bis (4-aminophenyl) sulfone, bis (3-amino-4-hydroxyphenyl) sulfone, 4,4′-bis (2-amino-6-methoxypyrimidyl) disulfone, 1,2-bis ( 2-aminoethoxy) ethane, 1,4-bis (4-aminophenoxy) One or more amines selected from benzene, bis (3-aminopropyl) ether and 4,4′-bis (4-aminophenoxy) biphenyl. Two or more of these may be used.

  Among these, the amine component comprised by the aliphatic hydrocarbon type which does not have an aromatic ring is preferable. Since the amine component composed of an aliphatic hydrocarbon system has flexibility, the adhesive force and the low warpage can be further improved.

Bis (3-aminopropyl) phosphate, phosphoric acid bisaminobutyl ester, bis (4-aminophenyl) pheosphate, bis (4-aminophenyl) phosphine, bis (3-amino-4-hydroxy) Phenyl) phosphine, bis (3-aminopropyl) sulfide, bis (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfone, bis (3-amino-4-hydroxyphenyl) sulfone, 4,4′-bis (2-amino-6-methoxypyrimidyl) disulfone, 1,2-bis (2-aminoethoxy) ethane, 1,4-bis (4-aminophenoxy) benzene, bis (3-aminopropyl) ether and 4 , 4′-bis (4-aminophenoxy) biphenyl The resin having a structural unit composed of an amine and dimer acid, ethylene diamine, hexamethylene diamine, piperazine and 1,4-bis one or more diamines and diethylenetriamine selected from (aminomethyl) cyclohexane, N, N' One or more aliphatic amines selected from one or more polyamines selected from bis (3-aminopropyl) ethylenediamine, N, N′ -bis (2-aminoethyl) -1,3-propanediamine and ethylenediaminehexamethylenetetramine ; Ru block copolymer der the structural unit composed of a dimer acid. One or more diamines selected from ethylenediamine, hexamethylenediamine, piperazine and 1,4-bis (aminomethyl) cyclohexane, and diethylenetriamine, N, N′-bis (3-aminopropyl) ethylenediamine, N, N′-bis (2 -By having a structural unit composed of one or more aliphatic amines selected from one or more polyamines selected from one or more polyamines selected from -aminoethyl) -1,3-propanediamine and ethylenediaminehexamethylenetetramine , And the insulation durability and heat deformation resistance under high temperature and high humidity conditions can be improved. In this case, bis (3-aminopropyl) phosphate, phosphoric acid bisaminobutyl ester, bis (4-aminophenyl) pheospheate, bis (4-aminophenyl) phosphine, bis (3-amino-4-) Hydroxyphenyl) phosphine, bis (3-aminopropyl) sulfide, bis (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfone, bis (3-amino-4-hydroxyphenyl) sulfone, 4,4′- Bis (2-amino-6-methoxypyrimidyl) disulfone, 1,2-bis (2-aminoethoxy) ethane, 1,4-bis (4-aminophenoxy) benzene, bis (3-aminopropyl) ether and Selected from 4,4'-bis (4-aminophenoxy) biphenyl Structural units (I) composed of the above amines with a dimer acid, ethylene diamine, hexamethylene diamine, piperazine and 1,4-bis one or more diamines and diethylenetriamine selected from (aminomethyl) cyclohexane, N, N ' One or more aliphatic amines selected from one or more polyamines selected from -bis (3-aminopropyl) ethylenediamine, N, N' -bis (2-aminoethyl) -1,3-propanediamine and ethylenediaminehexamethylenetetramine The copolymerization ratio of the structural unit (II) comprising dimer acid is preferably 0.4 ≦ (II / I) ≦ 32 (molar ratio). When the copolymerization ratio (II / I) is 0.4 or more, the insulation durability and heat distortion resistance are further improved, and when it is 32 or less, the adhesiveness and the low warpage are further improved. More preferably, 1.0 ≦ (II / I) ≦ 9.0.

Examples of the aliphatic amine having no phosphorus, sulfur, or oxygen include one or more diamines selected from ethylenediamine, hexamethylenediamine, piperazine and 1,4-bis (aminomethyl) cyclohexane, diethylenetriamine, N, N′-bis. It is one or more aliphatic amines selected from one or more polyamines selected from (3-aminopropyl) ethylenediamine, N, N′ -bis (2-aminoethyl) -1,3-propanediamine and ethylenediaminehexamethylenetetramine. . Two or more of these may be used.

  In the present invention, the amine value of the polyamide resin is preferably 5 or less, and more preferably 3 or less. When the amine value is 5 or less, the compatibility with the thermosetting resin described later is lowered and a fine phase separation structure is formed. Therefore, the balance between the adhesiveness and low warpage derived from the polyamide resin and the deformation heat resistance derived from the thermosetting resin can be improved. Here, the amine value of the polyamide resin is measured by titrating a solution obtained by dissolving 1 g of polyamide resin in a toluene / n-butanol (1/1 weight ratio) mixed solution with 0.1N hydrochloric acid and 0.1N potassium hydroxide. it can.

  Further, the iodine value of the dimer acid constituting the polyamide resin is preferably 20 or less, and more preferably 10 or less. The iodine value is indicated by the number of mg of iodine required for neutralizing an unsaturated bond group in 1 g of an unsaturated fatty acid. If the iodine value is 20 or less, warpage can be further reduced. Examples of the method for reducing the iodine value of dimer acid to 20 or less include, for example, the use of a raw fatty acid having an iodine value of 20 or less for the unsaturated bond group portion of a polyamide resin synthesized using dimer acid having a high iodine value. The method of hydrogenating reaction is mentioned. When two or more polyamide resins are contained, the average iodine value of all dimer acids contained in all polyamide resins is preferably 20 or less.

  Moreover, it is effective for the insulation improvement that the weight average molecular weight of a polyamide resin is 60,000 or more. This is because the electrical conductivity can be reduced by using a high molecular weight polyamide resin, and the weight average molecule is preferably 400,000 or less from the viewpoint of the solubility of the polyamide resin. The weight average molecular weight is a weight average molecular weight calculated from polystyrene conversion by GPC (gel permeation chromatography).

  The adhesive composition of the present invention contains a thermosetting resin. The content of the thermosetting resin is preferably 20 to 80% by weight, more preferably 30 to 70% by weight in the adhesive composition.

  Examples of the thermosetting resin include phenol resin, epoxy resin, urea resin, cyanate resin, maleimide resin, and acetal resin. From the viewpoint of heat distortion resistance and insulation, it is preferable to include a phenol resin and an epoxy resin.

  The phenol resin may be either a resol type or a novolac type. In addition to straight, it may be a phenol resin having various substituents such as cresol, tertiary butyl or nonyl, and two or more of these may be used.

  Among these, a resol resin having crosslinkability is particularly preferable because it improves heat distortion resistance and insulation durability. The resol resin having crosslinkability is a resol resin having a structural unit capable of forming a three-dimensional network structure when the resole resins are self-condensed to increase the molecular weight. Specifically, it is a resole resin having three or more reaction points excluding the phenolic hydroxyl group, and examples thereof include straight resole, m-alkyl substituted resole, bisphenol A resole, bisphenol S resole, and bisphenol F resole. Two or more kinds of these crosslinkable resole resins may be used. In addition, in order to achieve both heat distortion resistance, low warpage and adhesiveness, a resole in which a methylol group is added to a copolymer obtained by previously mixing and copolymerizing a phenol having crosslinkability and a phenol having linearity in a monomer state in advance. It is effective to use The content of the crosslinkable resole resin in the copolymerized resole resin is preferably 5 to 70% by weight, and more preferably 10 to 50% by weight. If it is 5% by weight or more, it is excellent in heat deformation resistance, and if it is 70% by weight or less, it is possible to suppress the decrease in adhesiveness and low warpage as much as possible. Moreover, 5-70 weight% is preferable and, as for content of the resol resin which has crosslinkability in a phenol resin, it is preferable that it is 10-50 weight%.

  The content of the phenol resin is preferably 5 to 200 parts by weight, more preferably 20 to 160 parts by weight with respect to 100 parts by weight of the polyamide resin.

  Moreover, using an epoxy resin as a thermosetting resin is effective for imparting adhesiveness.

  Examples of the epoxy resin include diglycidyl ethers such as bisphenol A, bisphenol F, bisphenol S, resorcinol, dihydroxynaphthalene, dicyclopentadiene diphenol, dicyclopentadiene dixylenol, epoxidized phenol novolac, epoxidized cresol novolak, and epoxidized. Trisphenylol methane, epoxidized tetraphenylol ethane, epoxidized metaxylene diamine and the like can be mentioned. Two or more of these may be used.

  In the adhesive composition for electronic parts of the present invention, the epoxy resin is preferably contained in an amount of 10 to 200 parts by weight, more preferably 20 to 180 parts by weight, still more preferably 30 to 160 parts by weight based on 100 parts by weight of the polyamide resin. Part. If it is 10 parts by weight or more, insulation reliability and adhesion durability are further improved, and if it is 200 parts by weight or less, flexibility is not impaired.

  The adhesive composition of the present invention may contain an epoxy resin curing agent. The epoxy resin curing agent is not particularly limited as long as it reacts with the epoxy resin, and examples thereof include known amine compounds, phenol resins, acid anhydrides, melamine resins, xylene resins, furan resins, and cyanate ester resins. Is done.

  The adhesive composition of the present invention may contain a curing accelerator. Curing accelerators include boron trifluoride amine complexes such as boron trifluoride triethylamine complex, 1,8-diazabicyclo (5.4.0) undecene-7, 2-alkyl-4-methylimidazole, dicyandiamide, Well-known things, such as a phenylphosphine and a sulfonium salt derivative, are mentioned. Two or more of these may be used. The content is preferably 0.1 to 20% by weight in the adhesive composition.

  The adhesive composition of the present invention may contain a compound having a plurality of functional groups in order to impart adhesiveness. For example, known compounds such as polyhydric alcohols such as glycerin, polyethylene glycol and polypropylene glycol, and compounds having a heterocyclic ring such as triazine, triazole and thiazole are exemplified.

  In addition to the above components, it is not limited at all to contain organic and inorganic components such as inorganic fillers, antioxidants and ion scavengers as long as the properties of the adhesive are not impaired.

  The adhesive sheet for electronic parts of the present invention (hereinafter referred to as adhesive sheet) has an adhesive layer formed from the adhesive composition for electronic parts of the present invention and at least one peelable protective film layer. Say. For example, a two-layer structure of protective film layer / adhesive layer or a three-layer structure of protective film layer / adhesive layer / protective film layer corresponds to this. Although the thickness of an adhesive bond layer can be suitably selected by the relationship with an elasticity modulus and a linear expansion coefficient, 2-500 micrometers is preferable, More preferably, it is 5-200 micrometers.

  The adhesive sheet may adjust the degree of curing of the adhesive layer by heat treatment. Adjustment of the degree of cure has the effect of preventing excessive flow of the adhesive when adhering the adhesive sheet to a wiring substrate or a semiconductor integrated circuit (IC) and preventing foaming due to moisture during heat curing.

  The protective film layer is not particularly limited as long as it can be peeled without impairing the form and function of the adhesive layer. For example, polyester, polyolefin, polyphenylene sulfide, polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polyvinyl A plastic film such as butyral, polyvinyl acetate, polyvinyl alcohol, polycarbonate, polyamide, polyimide, polymethyl methacrylate, a film obtained by coating a release agent such as silicone or fluorine compound on the film, and a paper laminated with these films, Examples include paper impregnated or coated with a releasable resin.

When the protective film layers are provided on both surfaces of the adhesive layer, F ₁ -F ₂ is 5 Nm ⁻ when the peeling force of each protective film layer on the adhesive layer is F ₁ , F ₂ (F ₁ > F ₂ ). ¹ or more is preferable, and 15 Nm ⁻¹ or more is more preferable. When F ₁ -F ₂ is larger than 5 Nm ⁻¹ , the protective film layer can be peeled with a stable peel surface. Further, the peeling forces F ₁ and F ₂ are preferably ¹ to 200 Nm ⁻¹ , more preferably 3 to 100 Nm ⁻¹ . If it is ¹ Nm ⁻¹ or more, the protective film layer is prevented from falling off, and if it is 200 Nm ⁻¹ or less, stable peeling is possible and the adhesive layer is not damaged.

  The tape with an adhesive for electronic parts of the present invention has an adhesive layer and an organic insulating film formed from the adhesive composition for electronic parts of the present invention. Examples of organic insulating films include so-called heat-resistant films such as polyimide, polyetherimide, polyamideimide, aromatic polyamide (aramid), polybenzoxazole, polyethylene naphthalate, and liquid crystal, or composites such as flexible epoxy / glass cloth. A material etc. are mentioned preferably. In particular, a polyimide film is particularly preferably used from the viewpoint of thermal dimensional stability.

  The copper-clad laminate of the present invention is formed by laminating an organic insulating film and a copper foil via an adhesive layer formed from the adhesive composition for electronic components of the present invention. Examples of the copper foil include electrolytic copper foil and rolled copper foil. Lamination of the copper foil is performed by laminating by a roll method or a press method under heating conditions.

  The substrate for connecting a semiconductor integrated circuit of the present invention uses the above-mentioned tape with an adhesive for electronic components or a copper-clad laminate, and a semiconductor device can be obtained using this.

  Next, a method for producing an adhesive composition for electronic parts according to the present invention, an adhesive sheet for electronic parts, a tape with an adhesive for electronic parts, a substrate for connecting a semiconductor integrated circuit, and a method for producing a semiconductor device are described as examples. Will be described.

(1) Adhesive composition for electronic parts A polyamide resin is added to a solvent heated to 30 to 70 ° C and dissolved while stirring for 30 minutes to 12 hours. After dissolution, the thermosetting resin is mixed under the same temperature range and dissolved while stirring for 30 minutes to 6 hours. After cooling to 40 ° C. or lower, a catalyst, other additives, and the like are added, and the mixture is filtered through a 1 to 30 μm filter to obtain a coating composition for an adhesive composition for electronic components. The solvent is not particularly limited, and examples thereof include aromatics such as toluene, xylene and chlorobenzene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aprotic polar solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. Two or more of these may be used.

(2) Adhesive sheet for electronic parts The paint of the adhesive composition for electronic parts obtained by the method described in (1) above is applied onto a polyester film (protective film) having releasability, dried, and then an adhesive. Form a layer. The drying conditions are generally 100 to 200 ° C. and 1 to 5 minutes. In order to increase the adhesive thickness, the adhesive layer may be laminated a plurality of times. Furthermore, an adhesive sheet is obtained by laminating a protective film layer of polyester or polyolefin having a releasability with low peel strength on the adhesive layer.

(3) Tape with adhesive for electronic parts One protective film of the adhesive sheet for electronic parts obtained by the method described in (2) above is peeled off, and a temperature of 100 to 160 ° C and a pressure of 0. By laminating at 1 to 0.3 MPa, a tape with an adhesive for electronic components can be obtained. Alternatively, the organic insulating film surface may be directly coated with the adhesive composition for electronic parts of the present invention. After lamination or coating, the degree of curing may be adjusted by heat treatment at 40 to 80 ° C. for about 20 to 300 hours, for example.

(4) Substrate for connecting a semiconductor integrated circuit When the tape with an adhesive for electronic components obtained by the method described in (3) above is used as a TAB tape, the tape with an adhesive for electronic components has a predetermined pattern. It punches with the press machine which installed the metal mold | die for punching which has, peels a protective film, performs copper foil lamination, and then heat-processes. The copper foil lamination conditions are preferably a temperature of 100 to 160 ° C. and a pressure of 0.1 to 0.3 MPa. The heating condition is preferably step heating, and it is preferable to raise the temperature to 150 to 180 ° C. finally while gradually raising the temperature from a relatively low temperature range of 50 to 90 ° C. Next, a semiconductor integrated circuit connecting substrate of the present invention can be obtained by forming a conductor circuit for connecting a semiconductor integrated circuit by photolithography.

(5) Copper-clad laminate After peeling the protective film of the adhesive tape for electronic parts obtained by the method described in (3) above and carrying out copper foil lamination, heat treatment is performed. A copper-clad laminate can be obtained. Copper foil laminating conditions and heating conditions are the same as in (3) above.

(6) Semiconductor device Using the substrate for connecting a semiconductor integrated circuit obtained by the method described in (4) above, wire bonding is preferably performed under conditions of 150 to 200 ° C., 50 to 200 Hz, and 1 second to 1 minute. The semiconductor device can be manufactured by connecting the semiconductor integrated circuits and then performing resin sealing with an epoxy sealant.

  As an example of a substrate for connecting a semiconductor integrated circuit, a TAB tape is shown in FIG. Sprocket holes 3 and device holes 4 are formed in the organic insulating film layer 1, and leads 5 are arranged on the pattern via the adhesive layer 2.

  The adhesive composition for electronic parts of the present invention includes a TAB pattern tape, a substrate for connecting a semiconductor integrated circuit such as a BGA package interposer, a copper-clad laminate, a die bonding material, a coverlay, a lead frame fixing tape, a LOC It is preferably used for producing a semiconductor device using a tape and a film-shaped adhesive such as an interlayer adhesive sheet of a multilayer substrate, and can be particularly preferably used for a BGA type semiconductor device.

  FIG. 2 shows one mode of a fine pitch-BGA using a BGA type semiconductor device. A semiconductor integrated circuit 7 is disposed on the organic insulating film 1 via a die bonding material 6, and the semiconductor integrated circuit 7 is connected to a gold wire via leads 5 and gold bumps 8 formed on the adhesive layer 2. 9 is connected. Solder balls 11 substantially corresponding to the number of pins of the IC are arranged in a grid (grid array), and the leads and the solder balls are connected. A solder resist is printed on the lead and is protected by the sealing resin 10.

  Hereinafter, an adhesive sheet using the adhesive composition for electronic parts of the present invention, a TAB tape, and the like will be specifically described as an example, but the present invention is not limited to these examples. The evaluation method will be described before the description of the examples.

[Evaluation method]
(1) Adhesive strength (A) Initial adhesive strength Using a TAB tape having a conductor width of 50 μm, the conductor was peeled in the direction of 90 ° at a speed of 50 mm / min, and the peeling force at that time was measured.
(B) Adhesive strength after high temperature treatment The TAB tape evaluated in (A) above was treated in a 150 ° C environment for 168 hours, and then the peel strength was measured under the same conditions as in (A).
(C) Retention rate The ratio of the peel force after the high temperature treatment to the peel force before (initial) the high temperature treatment was defined as the retention rate (%).

(2) Insulation durability 100V voltage is applied to TAB tape (conductor width 50μm, distance between conductors 50μm) in an environment of 130 ° C and 85% RH, and the time until the resistance decreases to 10 ⁶ Ω or less is measured. did.

(3) Storage modulus 5 to 8 adhesive layers of about 20 μm obtained by coating the adhesive composition were laminated to a thickness of about 100 to 150 μm, and then heated at 80 ° C. for 4 hours. The sample was heated to 4 ° C. over 4 hours and further heated at 160 ° C. for 4 hours to prepare a sample. Using this, the storage elastic modulus at 200 ° C. under a condition of a frequency of 1 Hz and a temperature rising rate of 5 ° C./min with a tensile mode dynamic viscoelasticity measuring device (RHEOVIBRON-DDV-25FP type, manufactured by Orientec Co., Ltd.) Was measured.

(4) Warpage The TAB tape was cut to 35 mm x 200 mm, and after the protective film was peeled off, an 18 µm electrolytic copper foil was laminated under conditions of 140 ° C, 0.2 MPa, and 1 m / min. Subsequently, a heat treatment was sequentially performed in an air oven at 80 ° C. for 3 hours, 100 ° C. for 5 hours, and 150 ° C. for 5 hours to obtain a warp evaluation sample. The obtained sample was conditioned at 23 ° C. and 55% RH for 24 hours according to SEMI-G76-0299, and the height of the opposite side of the sample that was warped up while holding one side of the sample was measured with a vernier caliper. (The case where the copper foil warps upward is defined as positive, and the case where the copper foil warps upward is defined as negative).

(Reference Example 1) Synthesis of polyamide resin (A-1 to 3) Dimer acid (trade name PRIPOL 1009, manufactured by Unikema Co., Ltd.) as an acid was 43 mol%, and bis (3-aminopropyl) phosphate was 58 mol% as an amine component. The reacted acid / amine reactant, antifoaming agent and 1 wt% phosphoric acid catalyst were stirred and heated at 140 ° C. for 1 hour, then heated to 205 ° C. and stirred for about 1.5 hours. The temperature was lowered by holding for 0.5 hour under a vacuum of about 2 kPa. Thereafter, an antioxidant (“Irganox” 1010, manufactured by Ciba-Gigi Co., Ltd.) was added to perform a dehydration polycondensation reaction to obtain a polyamide resin A-1 shown in Table 1. Further, the polyamide resin A-1 was subjected to a hydrogenation reaction in the presence of a catalyst so that the iodine value was 18 and 8, and polyamide resins A-2 and A-3 shown in Table 1 were obtained.

Reference Example 2 Synthesis of Polyamide Resin (A-4) Reference Example, except that bis (3-aminopropyl) sulfide was used as the amine component and the hydrogenation reaction was performed in the presence of a catalyst so that the iodine value was 44. In the same manner as in Example 1, a polyamide resin A-4 shown in Table 1 was obtained.

Reference Example 3 Synthesis of Polyamide Resin (A-5) Dimer acid (trade name PRIPOL 1009, manufactured by Unikema Co., Ltd.) (58 mol%) as an acid and bis (3-aminopropyl) sulfide (43 mol%) as an amine component were added. A polyamide resin A-5 shown in Table 1 was obtained in the same manner as in Reference Example 2 except that the hydrogenation reaction was performed in the presence of a catalyst so that the value was 42.

Reference Example 4 Synthesis of Polyamide Resin (A-6) Reference Example 3 except that the amount of phosphoric acid catalyst was 0.2% by weight and the hydrogenation reaction was performed in the presence of the catalyst so that the iodine value was 41. In the same manner, a polyamide resin A-6 shown in Table 1 was obtained.

(Reference Example 5)
Hydrogenation reaction in the presence of a catalyst so that the iodine value becomes 41 by adding 63 mol% of dimer acid (trade name PRIPOL1009, manufactured by Unikema) as acid and 38 mol% of bis (3-aminopropyl) sulfide as amine component A polyamide resin A-7 shown in Table 1 was obtained in the same manner as in Reference Example 2 except that

Reference Example 6 Synthesis of Polyamide Resin (A-8) Reference was made except that bis (4-aminophenyl) sulfide was used as an amine component and the hydrogenation reaction was carried out in the presence of a catalyst so that the iodine value was 43. In the same manner as in Example 3, polyamide resin A-8 shown in Table 1 was obtained.

Reference Example 7 Synthesis of Polyamide Resin (A-9) Reference was made except that bis (3-aminopropyl) ether was used as an amine component and a hydrogenation reaction was performed in the presence of a catalyst so that the iodine value was 44. In the same manner as in Example 3, polyamide resin A-9 shown in Table 1 was obtained.

Reference Example 8 Synthesis of Polyamide Resin (A-10-11) 43 mol% of dimer acid (trade name PRIPOL 1009, manufactured by Unikema Co., Ltd.) as an acid and 58 mol% of bis (3-aminopropyl) ether as an amine component were reacted. The acid / amine reactant, antifoaming agent and 2 wt% phosphoric acid catalyst were stirred and heated at 140 ° C. for 1 hour, then heated to 205 ° C. and stirred for about 1 hour. The temperature was lowered by holding for 0.5 hour under a vacuum of about 2 kPa. Thereafter, an antioxidant (“Irganox” 1010, manufactured by Ciba-Gaigi Co., Ltd.) was added, and a dehydration polycondensation reaction was performed to obtain polyamide oligomer 1.

  In addition, an acid / amine reaction product obtained by reacting 50 mol of dimer acid (trade name PRIPOL 1009, manufactured by Unikema Co., Ltd.) as an acid and 50 mol of hexamethylene diamine as an aliphatic diamine, an antifoaming agent and a 2 wt% phosphoric acid catalyst, After stirring and heating at 140 ° C. for 1 hour, the temperature was raised to 205 ° C. and stirring was continued for about 1 hour. The temperature was lowered by holding for 0.5 hour under a vacuum of about 2 kPa. Thereafter, an antioxidant (“Irganox” 1010, manufactured by Ciba-Gaigi Co., Ltd.) was added, and a dehydration polycondensation reaction was performed to obtain polyamide oligomer 2.

  Polyamide oligomer 1 / Polyamide oligomer 2 = 50 mol / 50 mol, 95 mol / 5 mol mixed, phosphoric acid catalyst is added in the same way as the oligomer production, and heated after stirring and heating, dehydration polycondensation reaction Then, hydrogenation reaction was carried out in the presence of a catalyst so that the iodine values were 45 and 46, and polyamide resins A-10 and A-11 shown in Table 1 were obtained, respectively.

(Reference Example 8) Synthesis of Polyamide Resin (A-12) Acid / amine reaction product obtained by reacting 43 mol% of dimer acid (trade name PRIPOL 1009, manufactured by Unikema Co., Ltd.) as an acid and 58 mol% of hexamethylenediamine as an aliphatic diamine The antifoaming agent and 1 wt% phosphoric acid catalyst were stirred and heated at 140 ° C. for 1 hour, then heated to 205 ° C. and stirred for about 1.5 hours. The temperature was lowered by holding for 0.5 hour under a vacuum of about 2 kPa. Thereafter, an antioxidant (“Irganox” 1010, manufactured by Ciba-Gaigi Co., Ltd.) was added to perform a dehydration polycondensation reaction, and a hydrogenation reaction was performed in the presence of a catalyst so that the iodine value was 48. -12 was obtained.

( Reference Example 1)
(A) Production of adhesive sheet for electronic parts Polyamide resin A-1 and epoxy resin B-2 obtained in Reference Example 1 (manufactured by JER Corporation, “Epicoat” (registered trademark) 828), are shown in Table 2. Phenol resin B-2 (manufactured by Showa High Polymer Co., Ltd., “Shonol” (registered trademark) BKM 2620) and DBU (manufactured by San Apro Co.) as a curing catalyst were blended as shown in Table 3, respectively, and the solid content was 20% by weight. In this way, an adhesive solution was prepared by stirring and mixing in a mixed solvent of methanol / toluene = 20/80 at 30 ° C. This adhesive solution was applied to a protective film (“Film Vinner” GT (registered trademark) manufactured by Fujimori Kogyo Co., Ltd.), which had been subjected to a release treatment, with a bar coater so as to have a dry thickness of about 12 μm. It dried for minutes and produced the adhesive sheet for electronic components.

(B) Production of TAB tape The adhesive sheet for electronic parts obtained by the method described in (a) above was laminated on a polyimide film having a thickness of 75 μm under conditions of 140 ° C., 0.2 MPa, 1 m / min, and TAB. A tape was prepared.

(C) Production of a substrate for connecting a semiconductor integrated circuit The protective film of the TAB tape obtained by the method described in (b) above was peeled off, and an 18 μm electrolytic copper foil was obtained at 140 ° C., 0.2 MPa, 1 m / min. Lamination was performed under the following conditions. Subsequently, a heat treatment was sequentially performed in an air oven at 80 ° C. for 3 hours, at 100 ° C. for 5 hours, and at 150 ° C. for 5 hours to produce a TAB tape with copper foil. Photoresist film formation, etching, resist stripping, and electrolytic gold plating were performed on the copper foil surface of the obtained TAB tape with copper foil by a conventional method to prepare an evaluation sample and a semiconductor device connection substrate. The nickel plating thickness was 3 μm, and the gold plating thickness was 1 μm.

(D) Fabrication of semiconductor device A 20 mm square IC was pressure-bonded to the substrate for connecting a semiconductor integrated circuit obtained by the method described in (c) above using a die bonding material (LE-5000, manufactured by Lintec Corporation). . In this state, heat curing was performed at 160 ° C. for 30 minutes. Next, the IC and the wiring substrate were wire-bonded with a gold wire having a diameter of 25 μm under the conditions of 180 ° C. and 110 kHz, and then sealed with resin. Finally, solder balls were mounted by reflow to obtain a semiconductor device as shown in FIG.

(Examples 2 to 4, Reference Examples 2 to 14 , Comparative Example 1)
An adhesive sheet for electronic parts, a TAB tape, a semiconductor integrated circuit connection substrate, and a semiconductor device were obtained in the same manner as in Reference Example 1 except that the adhesive composition was changed as shown in Tables 3 to 5.

(Comparative Examples 2 to 4)
As a polyamide resin, “Pebax” (registered trademark) manufactured by Arkema Co., Ltd. was used in Comparative Example 2, and “TPAE-12” (registered trademark) manufactured by Fuji Kasei Kogyo Co., Ltd. was used as Comparative Example 3. In Comparative Example 4, an electronic component was used in the same manner as in Reference Example 1 except that Toto Kasei Co., Ltd. ("Epototo" (registered trademark) YDC1312) was used and the adhesive composition was changed as shown in Table 5. An adhesive sheet, a TAB tape, a semiconductor integrated circuit connecting substrate and a semiconductor device were obtained.

Tables 3 to 5 show the adhesive composition and evaluation results of each of the examples, reference examples, and comparative examples.

It is the schematic which shows the one aspect | mode of the TAB tape. It is sectional drawing which shows the one aspect | mode of the fine pitch-BGA using a BGA type semiconductor device.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Organic insulating film 2 Adhesive layer 3 Sprocket hole 4 Device hole 5 Lead 6 Die bonding material 7 Semiconductor integrated circuit 8 Gold bump 9 Gold wire 10 Sealing resin 11 Solder ball

Claims (8)

Bis (3-aminopropyl) phosphate, Phosphoacid acid bisaminobutyl ester, Bis (4-aminophenyl) pheospheate, Bis (4-aminophenyl) phosphine, Bis (3-amino-4-hydroxyphenyl) Phosphine, bis (3-aminopropyl) sulfide, bis (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfone, bis (3-amino-4-hydroxyphenyl) sulfone, 4,4′-bis (2 -Amino-6-methoxypyrimidyl) disulfone, 1,2-bis (2-aminoethoxy) ethane, 1,4-bis (4-aminophenoxy) benzene, bis (3-aminopropyl) ether and 4,4 One or more of the compounds selected from '-bis (4-aminophenoxy) biphenyl A structural unit composed of ethylene and dimer acid, one or more diamines selected from ethylenediamine, hexamethylenediamine, piperazine and 1,4-bis (aminomethyl) cyclohexane, and diethylenetriamine, N, N′-bis (3- Aminopropyl) from ethylenediamine, N, N′-bis (2-aminoethyl) -1,3-propanediamine and one or more aliphatic amines selected from one or more polyamines selected from ethylenediaminehexamethylenetetramine and dimer acid. An adhesive composition for electronic parts , comprising a polyamide resin , which is a block copolymer having a structural unit, and a thermosetting resin. Claim 1 Symbol mounting adhesive composition for electronic components of, wherein the amine value of the polyamide resin is 5 or less. The adhesive composition for electronic components according to claim 1 or 2, wherein the dimer acid constituting the polyamide resin has an iodine value of 20 or less. The said thermosetting resin contains a phenol resin, The adhesive composition for electronic components in any one of Claims 1-3 characterized by the above-mentioned. The adhesive sheet for electronic components containing the adhesive bond layer formed from the adhesive composition for electronic components in any one of Claims 1-4, and at least one layer of protective film layer which can be released. The tape with an adhesive for electronic components which has an adhesive bond layer formed from the adhesive composition for electronic components in any one of Claims 1-4, and an organic insulating film. A substrate for connecting a semiconductor integrated circuit using the adhesive sheet for electronic parts according to claim 5 . The copper clad laminated board formed by laminating | stacking an organic insulating film and copper foil through the adhesive bond layer formed from the adhesive composition for electronic components in any one of Claims 1-4 .

Images